CN103730601A - Bragg reflection reflector distribution structure, preparation method thereof and organic light-emitting diode structure - Google Patents
Bragg reflection reflector distribution structure, preparation method thereof and organic light-emitting diode structure Download PDFInfo
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Abstract
The invention provides a Bragg reflection reflector distribution structure. The Bragg reflection reflector distribution structure comprises high-refractive-index layers and low-refractive-index layers, wherein the high-refractive-index layers and the low-refractive-index layers do not absorb visible light and are arranged alternately in the thickness direction of the Bragg reflection reflector distribution structure. The low-refractive-index layers are made of organic polymer and the refractive index of the low-refractive-index layers is no larger than 1.4. The invention further provides a preparation method of the Bragg reflection reflector distribution structure and an organic light-emitting diode comprising the Bragg reflection reflector distribution structure. The low-refractive-index layers are made of the organic polymer, so that when the low-refractive-index layers are prepared, the technology is relatively simple, time cost needed for manufacture of the Bragg reflection reflector distribution structure is reduced, and the production efficiency is improved. Due to the fact that the low-refractive-index layers and the high-refractive-index layers do not absorb the visible light, the Bragg reflection reflector distribution structure can be applied to common organic light-emitting diodes.
Description
Technical field
The present invention relates to organic luminescent device field, particularly, relate to the preparation method of a kind of distribution Bragg reflector structure, this distribution Bragg reflector structure and comprise the Organic Light Emitting Diode of described distribution Bragg reflector structure.
Background technology
The light extraction efficiency of common organic light emitting diode device is only 20% left and right, in order to improve the light emission rate of organic light emitting diode device, distribution Bragg reflector structure is set on the exiting surface of Organic Light Emitting Diode conventionally.
Conventionally, distribution Bragg reflector structure comprises the high refractive index layer and the low-index layer that are arranged alternately, and low-index layer is conventionally by the SiO that does not absorb visible ray
2/ SiNx makes, and high refractive index layer is conventionally by the SiO that does not absorb visible ray
2/ TiO
2make.But high refractive index layer and low-index layer are inorganic matter, need in substrate, form high refractive index layer and low-index layer by complicated sputtering technology, process costs is high.
In addition, can utilize respectively organic polymer PVK and PAA to make high refractive index layer and low-index layer, but PVK and PAA absorb visible ray, can only be applied to tiny cavity light-emitting diode and laser.
Therefore, how by simple technique, to make for the distribution Bragg reflector structure of Organic Light Emitting Diode and to become this area technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of distribution Bragg reflector structure, this distribution Bragg reflector structure and comprise the Organic Light Emitting Diode of described distribution Bragg reflector structure.Can utilize simple technique to make described distribution Bragg reflector structure.
To achieve these goals, as one aspect of the present invention, a kind of distribution Bragg reflector structure is provided, described distribution Bragg reflector structure comprises the high refractive index layer that does not absorb visible ray being arranged alternately along the thickness direction of described distribution Bragg reflector structure and the low-index layer that does not absorb visible ray, wherein, described low-index layer is made by organic polymer, and the refractive index of described low-index layer is not more than 1.5.
Preferably, the poly methyl methacrylate polymer that described low-index layer is crosslinking curing.
Preferably, described high refractive index layer comprises matrix and is entrained in the inorganic nanoparticles in described matrix, the refractive index of described inorganic nanoparticles is not less than 2.0, and described matrix is made by organic polymer, the refractive index at least large 0.1 of low-index layer described in the refractive index ratio of described high refractive index layer.
Preferably, the material that forms the matrix in described high refractive index layer is identical with the material that forms described low-index layer.
Preferably, described inorganic nanoparticles comprises one or more in nitride, titanium dioxide and the tantalum pentoxide of silicon.
As another aspect of the present invention, a kind of organic LED structure is provided, this organic LED structure includes OLED and is arranged on the distribution Bragg reflector structure of the exiting surface of described Organic Light Emitting Diode, wherein, described distribution Bragg reflector structure is above-mentioned distribution Bragg reflector structure provided by the present invention.
Preferably, according to following formula, calculate the thickness of described high refractive index layer:
D
1=λ/4n
1, wherein, d
1for the thickness of described high refractive index layer, λ is the wavelength of the light that sends of described Organic Light Emitting Diode, n
1for the refractive index of high refractive index layer;
According to following formula, calculate the thickness of described low-index layer:
D
2=λ/4n
2, wherein, d
2for the thickness of described low-index layer, λ is the wavelength of the light that sends of described Organic Light Emitting Diode, n
2for the refractive index of low-index layer.
As another aspect of the present invention, a kind of preparation method of distribution Bragg reflector structure is provided, wherein, described preparation method comprises and alternately carries out following steps, to form along the low-index layer being arranged alternately on the thickness direction of described distribution Bragg reflector structure and high refractive index layer:
S1, utilize organic polymer to make not absorb the low-index layer of visible ray, the refractive index of described low-index layer is not more than 1.5;
S2, formation do not absorb the high refractive index layer of visible ray.
Preferably, described step S1 comprises:
S11, in substrate, coating comprises the mixture of poly methyl methacrylate polymer;
S12, make to comprise and the mixture crosslinking curing of described poly methyl methacrylate polymer form described low-index layer.
Preferably, in described step S12, the mixture that comprises described poly methyl methacrylate polymer is heated, so that the mixture crosslinking curing of described poly methyl methacrylate polymer.
Preferably, described step S2 comprises:
S21, to including the inorganic nanoparticles that adulterates in the mixture of organic polymer, the refractive index of described inorganic nanoparticles is not less than 2.0;
S22, will be coated on described low-index layer doped with the mixture that includes organic polymer of inorganic nanoparticles, and make the organic polymer crosslinking curing doped with inorganic nanoparticles, to form described high refractive index layer, this high refractive index layer includes the substrate that organic polymer crosslinking curing obtains and is distributed in the inorganic nanoparticles in described substrate, cuts the refractive index at least large 0.1 of low-index layer described in the refractive index ratio of described high refractive index layer.
Preferably, the organic polymer in described step S22 is identical with the organic polymer of making described low-index layer.
Preferably, described inorganic nanoparticles comprises one or more in nitride, titanium dioxide and the tantalum pentoxide of silicon.
Because low-index layer is made by organic polymer, therefore, when preparing low-index layer, technique is relatively simple, thereby reduced, manufactures the required time cost of described distribution Bragg reflector structure, has improved production efficiency.And because described low-index layer and described high refractive index layer all do not absorb visible ray, so distribution Bragg reflector structure provided by the present invention can be for common Organic Light Emitting Diode.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the schematic diagram of distribution Bragg reflector structure provided by the present invention.
Fig. 2 is the preparation method's of the distribution Bragg reflector structure shown in construction drawing 1 flow chart.
Description of reference numerals
10: low-index layer 20: high refractive index layer
30: glass substrate
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
As shown in Figure 1, as one aspect of the present invention, a kind of distribution Bragg reflector structure is provided, described distribution Bragg reflector structure comprises the high refractive index layer that does not absorb visible ray 20 being arranged alternately along the thickness direction of described distribution Bragg reflector structure and the low-index layer 10 that does not absorb visible ray, wherein, low-index layer 10 is made by organic polymer, and the refractive index of low-index layer 10 is not more than 1.5.
Because low-index layer 10 is made by organic polymer, therefore, when preparing low-index layer 10, technique is relatively simple, thereby reduced, manufactures the required time cost of described distribution Bragg reflector structure, has improved production efficiency.For example, organic polymer can be coated on substrate, then carry out crosslinking curing, form low-index layer 10.Because low-index layer 10 and high refractive index layer 20 all do not absorb visible ray, therefore, distribution Bragg reflector structure provided by the present invention can be for Organic Light Emitting Diode.
Should be understood that, " substrate " described herein can be the glass substrate 30 that low-index layer 10 and high refractive index layer 20 are not set, and can be also the glass substrate that is provided with low-index layer 10 and/or high refractive index layer 20.And, in the present invention, the number of plies of low-index layer 10 and high refractive index layer 20 is also not specifically limited, but should guarantees that described distribution Bragg reflector structure comprises at least one deck low-index layer 10 and at least one floor height index layer 20.Although only define the refractive index of low-index layer 10, be not more than 1.5, but, low-index layer 10 should be realized the function of described distribution Bragg reflector structure,, coordinate with high refractive index layer 20, improve the light extraction efficiency of Organic Light Emitting Diode, and the spectrum of Organic Light Emitting Diode is narrowed, thereby make the color saturation of the light that Organic Light Emitting Diode sends higher.
In the present invention, to making the material of high refractive index layer 20, do not have special restriction, for example, can utilize inorganic matter SiO
2/ TiO
2make high refractive index layer 20, also can utilize refractive index to make high refractive index layer 20 higher than low-index layer 10 and the organic substance that do not absorb visible ray, specifically will be described herein-after, first do not repeat here.
In the present invention, the material that forms low-index layer 10 is also not particularly limited, for example, can carries out crosslinking curing to poly methyl methacrylate polymer (PMMA), form low-index layer 10.Certainly, also can adopt polyethylene, poly(ethylene oxide), polymethyl siloxane etc. to form low-index layer 10.
As a kind of preferred implementation of high refractive index layer 20, this high refractive index layer 20 can comprise matrix and be entrained in the inorganic nanoparticles in described matrix, the refractive index of described inorganic nanoparticles is not less than 2.0, described matrix is made by organic polymer, the refractive index at least large 0.1 of low-index layer described in the refractive index ratio of described high refractive index layer.
When high refractive index layer 20 adopts above-mentioned execution mode; can first inorganic nanoparticles be blended in the organic polymer of making matrix; then inorganic nanoparticles and organic polymer are coated on substrate; make described organic polymer crosslinking curing, thereby can obtain having the high refractive index layer 20 of mentioned component.Hence one can see that, can utilize simple technique to prepare high refractive index layer 20.
In order to simplify preparation technology, preferably, the material that forms the matrix in high refractive index layer 20 can be identical with the material that forms low-index layer 10.For example, when utilizing poly methyl methacrylate polymer to prepare low-index layer 10, also can utilize poly methyl methacrylate polymer to prepare the matrix of high refractive index layer 20.
In the above-described embodiment, can utilize similar technological parameter to prepare high refractive index layer 20 and low-index layer 10, thereby simplify preparation technology, improve production efficiency.
The major function of the inorganic nanoparticles in high refractive index layer 20 is the refractive index that increases high refractive index layer 20, thereby make material at base material and low-index layer 10 identical, the refractive index of high refractive index layer 20 can be greater than the refractive index of low-index layer 10.In the present invention, described inorganic nanoparticles can be selected from nitride (SiNx), the titanium dioxide (TiO of silicon
2) and tantalum pentoxide (Ta
2o
5) in one or more.
As another aspect of the present invention, a kind of organic LED structure is provided, this organic LED structure includes OLED and is arranged on the distribution Bragg reflector structure of the exiting surface of described Organic Light Emitting Diode, wherein, described distribution Bragg reflector structure is above-mentioned distribution Bragg reflector structure provided by the present invention.
High refractive index layer 20 in described distribution Bragg reflector structure and low-index layer 10 all do not absorb visible ray, therefore can be applied to common Organic Light Emitting Diode, to improve the light extraction efficiency of Organic Light Emitting Diode, the color saturation of the colored light that increase Organic Light Emitting Diode sends.And described distribution Bragg reflector structure preparation technology is simple, can reduce the process costs of described organic LED structure, improve the overall manufacturing efficiency of described organic LED structure.
Different Organic Light Emitting Diodes can send the light of different colours, can determine according to the color of the light of Organic Light Emitting Diode the thickness of high refractive index layer 20 and low-index layer 10 in described distribution Bragg reflector.
Particularly, can calculate according to following formula (1) thickness d of described high refractive index layer
1:
d
1=λ/4n
1 （1）
Wherein, λ is the wavelength of the light that sends of described Organic Light Emitting Diode;
N
1for the refractive index of high refractive index layer.
And, can calculate according to following formula (1) thickness d of described low-index layer
2:
d
2=λ/4n
2 （2）
Wherein, λ is the wavelength of the light that sends of described Organic Light Emitting Diode;
N
2for the refractive index of low-index layer.
Above-mentioned computing formula is when utilizing inorganic material to manufacture described distribution Bragg reflector structure, and the formula of thickness that calculates high refractive index layer and low-index layer is identical, and Computing Principle is also identical, repeats no more here.
As another aspect of the present invention, as shown in Figure 2, a kind of preparation method of distribution Bragg reflector structure is provided, wherein, described preparation method comprises and alternately carries out following steps, to form along the low-index layer being arranged alternately on the thickness direction of described distribution Bragg reflector structure and high refractive index layer:
S1, utilize organic polymer to make not absorb the low-index layer of visible ray, the refractive index of described low-index layer is not more than 1.5;
S2, formation do not absorb the high refractive index layer of visible ray.
As noted before, the materials and methods that forms described high refractive index layer is all not particularly limited, as long as the refractive index of the high refractive index layer forming is greater than the refractive index of described low-index layer herein.
Compared with inorganic material being deposited in substrate with the method for utilizing sputter, utilize organic polymer to make low-refraction layer process simple, equipment cost is lower, and hence one can see that, and preparation method provided by the present invention has relatively high production efficiency.
When described organic polymer is poly methyl methacrylate polymer, described step S1 can comprise:
S11, in substrate, coating comprises the mixture of poly methyl methacrylate polymer;
S12, make to comprise and the mixture crosslinking curing of described poly methyl methacrylate polymer form described low-index layer.
Hold intelligiblely, described mixture can also comprise organic solvent and curing agent etc. except comprising poly methyl methacrylate polymer.
Preferably, in described step S12, the mixture that comprises described poly methyl methacrylate polymer is heated, so that the mixture crosslinking curing of described poly methyl methacrylate polymer.
In described step S12, be heated to rare below two: (1), make to comprise poly methyl methacrylate polymer crosslinking curing; (2) remove the organic solvent in described mixture.
When after poly methyl methacrylate polymer crosslinking curing, when on this layer of low-index layer, coating forms the mixture that includes organic polymer of substrate of high refractive index layer, the organic solvent in this mixture can not dissolve low-index layer.
Preferably, in described step S11, use spin coating proceeding that the mixture that comprises poly methyl methacrylate polymer is coated on substrate.Spin coating proceeding can accurately be controlled the thickness of the mixture that comprises poly methyl methacrylate polymer, thereby can accurately control the thickness of described low-index layer.
Particularly, described step S2 can comprise:
S21, to including the inorganic nanoparticles that adulterates in the mixture of organic polymer, the refractive index of described inorganic nanoparticles is not less than 2.0;
S22, will be coated on described low-index layer doped with the mixture that includes organic polymer of inorganic nanoparticles, and make the organic polymer crosslinking curing doped with inorganic nanoparticles, to form described high refractive index layer, this high refractive index layer includes the substrate that organic polymer crosslinking curing obtains and is distributed in the inorganic nanoparticles in described substrate, cuts the refractive index at least large 0.1 of low-index layer described in the refractive index ratio of described high refractive index layer.
Hold intelligiblely, in step S21, include in the mixture of organic polymer and can also comprise organic solvent and curing agent etc.
In order to simplify preparation technology, the organic polymer in described step S22 is identical with the organic polymer of making described low-index layer.
Therefore, also can utilize spin coating proceeding that the mixture doped with inorganic nanoparticles in described step S22 is coated on substrate.And, in step S22, also can utilize the method for heating to make organic polymer crosslinking curing.
Certainly, also can utilize different organic polymer materials to prepare respectively the matrix of low-index layer and high index of refraction etc.It should be noted in the discussion above that in adjacent high refractive index layer and low-index layer, in the time of should using different dicyandiamide solution control spin coating last layer polymer, lower one layer of polymeric is not caused to dissolving.
As one embodiment of the present invention, described inorganic nanoparticles can comprise one or more in nitride, titanium dioxide and the tantalum pentoxide of silicon.
Be understandable that, above execution mode is only used to principle of the present invention is described and the illustrative embodiments that adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (13)
1. a distribution Bragg reflector structure, described distribution Bragg reflector structure comprises the high refractive index layer that does not absorb visible ray being arranged alternately along the thickness direction of described distribution Bragg reflector structure and the low-index layer that does not absorb visible ray, it is characterized in that, described low-index layer is made by organic polymer, and the refractive index of described low-index layer is not more than 1.5.
2. distribution Bragg reflector structure according to claim 1, is characterized in that, the poly methyl methacrylate polymer that described low-index layer is crosslinking curing.
3. distribution Bragg reflector structure according to claim 1 and 2, it is characterized in that, described high refractive index layer comprises matrix and is entrained in the inorganic nanoparticles in described matrix, the refractive index of described inorganic nanoparticles is not less than 2.0, described matrix is made by organic polymer, the refractive index at least large 0.1 of low-index layer described in the refractive index ratio of described high refractive index layer.
4. distribution Bragg reflector structure according to claim 3, is characterized in that, the material that forms the matrix in described high refractive index layer is identical with the material that forms described low-index layer.
5. distribution Bragg reflector structure according to claim 3, is characterized in that, described inorganic nanoparticles comprises one or more in nitride, titanium dioxide and the tantalum pentoxide of silicon.
6. an organic LED structure, this organic LED structure includes OLED and is arranged on the distribution Bragg reflector structure of the exiting surface of described Organic Light Emitting Diode, it is characterized in that, described distribution Bragg reflector structure is the distribution Bragg reflector structure described in any one in claim 1 to 5.
7. organic LED structure according to claim 6, is characterized in that, calculates the thickness of described high refractive index layer according to following formula:
D
1=λ/4n
1, wherein, d
1for the thickness of described high refractive index layer, λ is the wavelength of the light that sends of described Organic Light Emitting Diode, n
1for the refractive index of high refractive index layer;
According to following formula, calculate the thickness of described low-index layer:
D
2=λ/4n
2, wherein, d
2for the thickness of described low-index layer, λ is the wavelength of the light that sends of described Organic Light Emitting Diode, n
2for the refractive index of low-index layer.
8. the preparation method of a distribution Bragg reflector structure, it is characterized in that, described preparation method comprises and alternately carries out following steps, to form along the low-index layer being arranged alternately on the thickness direction of described distribution Bragg reflector structure and high refractive index layer:
S1, utilize organic polymer to make not absorb the low-index layer of visible ray, the refractive index of described low-index layer is not more than 1.5;
S2, formation do not absorb the high refractive index layer of visible ray.
9. preparation method according to claim 8, is characterized in that, described step S1 comprises:
S11, in substrate, coating comprises the mixture of poly methyl methacrylate polymer;
S12, make to comprise and the mixture crosslinking curing of described poly methyl methacrylate polymer form described low-index layer.
10. preparation method according to claim 9, is characterized in that, in described step S12, the mixture that comprises described poly methyl methacrylate polymer is heated, so that the mixture crosslinking curing of described poly methyl methacrylate polymer.
Preparation method in 11. according to Claim 8 to 10 described in any one, is characterized in that, described step S2 comprises:
S21, to including the inorganic nanoparticles that adulterates in the mixture of organic polymer, the refractive index of described inorganic nanoparticles is not less than 2.0;
S22, will be coated on described low-index layer doped with the mixture that includes organic polymer of inorganic nanoparticles, and make the organic polymer crosslinking curing doped with inorganic nanoparticles, to form described high refractive index layer, this high refractive index layer includes the substrate that organic polymer crosslinking curing obtains and is distributed in the inorganic nanoparticles in described substrate, cuts the refractive index at least large 0.1 of low-index layer described in the refractive index ratio of described high refractive index layer.
12. preparation methods according to claim 11, is characterized in that, the organic polymer in described step S22 is identical with the organic polymer of making described low-index layer.
13. preparation methods according to claim 11, is characterized in that, described inorganic nanoparticles comprises one or more in nitride, titanium dioxide and the tantalum pentoxide of silicon.
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| CN110323348A (en) * | 2019-07-01 | 2019-10-11 | 南方科技大学 | Top-emission quantum dot light-emitting device, preparation method thereof and display device |
| CN111081896A (en) * | 2019-12-04 | 2020-04-28 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
| WO2021109225A1 (en) * | 2019-12-04 | 2021-06-10 | 深圳市华星光电半导体显示技术有限公司 | Display panel and method for manufacturing same |
| US11515508B2 (en) * | 2019-12-04 | 2022-11-29 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Display panel and manufacturing method thereof |
| CN111063826A (en) * | 2019-12-16 | 2020-04-24 | 深圳市华星光电半导体显示技术有限公司 | Display panel |
| US11121342B2 (en) | 2019-12-16 | 2021-09-14 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Display panel having a nano-stack layer |
| CN113189823B (en) * | 2021-04-22 | 2022-04-26 | 上海大学 | Color electronic paper |
| CN113189823A (en) * | 2021-04-22 | 2021-07-30 | 上海大学 | Color electronic paper |
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